Stable and pumpable liquid aluminum chloride and bromide complexes

ABSTRACT

SOLUTIONS OF ALUMINUM CHLORIDE OR ALUMINUM BROMIDE, IN MOLAR EXCESS, IN METHYL ESTERS IF CERTAIN NORMAL AND BRANCHED-CHAIN ALKANOIC ACIDS REMAIN STABLE AND PUMPABLE AT LEAST 20 DAYS OR MORE. THESE SOLUTIONS ARE USEFUL CATALYSTS FOR REACTIONS, SUCH AS OLEFIN POLYMERIZATION OR ETHYLATION OF ISOBUTANE, AND CAN BE RECOVERED AND RECYCLED.

Kinematic Viscosity @|OO F., cs.

p 3, 1974 .1. A. BRENNAN STABLE AND PUMEABLE LIQUID ALUMINUM CHLORIDEANDBROMIDE COMPLEXES Filed Sept. 8, 1972 04 4 01 on \1 00mg 25 DaysUnited States Patent 3,833,678 STABLE AND PUMPABLE LIQUID ALUMINUMCHLORIDE AND BROMIDE COMPLEXES James A. Brennan, Cherry Hill, N.J.,assignor to Mobil Oil Corporation Continuation-impart of applicationSer. No. 41,709, May

27, 1970, now Patent No. 3,725,498, which is a continuation ofapplication Ser. No. 745,415, July 17, 1968, which is acontinuation-in-part of application Ser. No. 598,564, Oct. 17, 1966,which in turn is a continuation-in-part of application Ser. No. 334,394,Dec. 30, 1963, all now abandoned. This application Sept. 8, 1972, Ser.No. 287,303

Int. Cl. C07c 3/18 US. Cl. 260683.15 B 12 Claims ABSTRACT OF THEDISCLOSURE Solutions of aluminum chloride or aluminum bromide, in molarexcess, in methyl esters of certain normal and branched-chain alkanoicacids remain stable and pumpable at least 20 days or more. Thesesolutions are useful catalysts for reactions, such as olefinpolymerization or ethylation of isobutane, and can be recovered andrecycled.

REFERENCES TO RELATED APPLICATIONS This application is acontinuation-in-part of copending application Ser. No. 41,709 filed May27, 1970, now US. Pat. No. 3,725,498, a continuation of abandonedapplication Ser. No. 745,415 filed July 17, 1968, a continuation-in-partof abandoned application Ser. No. 598,564, filed Oct. 17, 1966, acontinuation-in-part of abandoned application Ser. No. 334,394, filedDec. 30, 1963.

BACKGROUND OF THE INVENTION Field of the Invention This inventionrelates to liquid aluminum halide catalysts that effect excellentcontrol, uniformity, and reproducibility in reactions catalyzed byaluminum halide, and which remain stable and pumpable liquids over longperiods of time.

Description of the Prior Art As is well known to those familiar with theart, aluminum halides, particularly aluminum chloride and bromide, havebeen proposed as catalysts in many reactions, including polymerization,alkylation, and isomerization. As aluminum chloride (also aluminumbromide) is a solid, whereas the reactants are liquids, it has beendiflicult to control reactions and to obtain reproducible results. Forexample, the polymerization of olefins has been carried out by severalmethods, each of which has disadvantages: (1) All the olefin is added tothe catalyst, resulting in an uncontrollable exothermic reaction. (2)The olefin is added slowly to the catalyst,

which means that the catalyst concentration varies dur- 3,833,678Patented Sept. 3, 1974 the difiiculty inherent in obtaining uniformcontact between solid catalyst and liquid olefin.

If, on the other hand, both the catalyst and reactants are liquid,uniform contact is attained and accurate metering is readilyaccomplished. Thus, the ditficulties encountered in the use of solidaluminum chloride or bromide could be substantially eliminated, if thealuminum chloride or bromide could be obtained in acatalytically-active, liquid form. It has been proposed to dissolve (orcomplex) aluminum chloride in various solvents, such as alcohols,ethers, and methyl acetate. In each case, however, less than one mole ofaluminum chloride was dissolved per mole of solvent. Such molar ratiosolutions were not catalytically active.

In application Ser. No. 334,394 it was generally disclosed that catalystsolutions containing more than one mole of an aluminum halide dissolvedin certain esters could be used to polymerize olefins and that suchsolutions could be recycled to subsequent runs. It has also beenproposed to isomerize n-pentane using AlCl dissolved in ethyl acetate,decanting reaction product and re-using the catalyst solution insubsequent runs [Ind. & Eng. Chem, 42, 342 (1950)]. In both theaforementioned polymerization and isomerization recycling runs, thesolvent was ethyl acetate and all runs were carried out withintwenty-four hours.

It was found, as a result of pilot plant runs, that at temperatures of2025 C. the AlCl -ethyl acetate catalyst solution decomposed within24-30 hours, with the evolution of HCl, to a hard solid. Hence, thecatalyst solution," as previously anticipated, was not recyclable overprolonged periods of several days or months. In application Ser. No.598,564 it was disclosed that of many ester solvents for aluminumhalide, ethyl propionate was the only ester found so far, whichmaintains the aluminum halide in liquid solution for prolonged periods,i.e., more than two days and up to a month or more.

Ethyl propionate solutions of aluminum halide were specificallydisclosed in parent application Ser. No. 334,394 and in thecorresponding French Pat. No. 1,433,373. It has now been found thatsolutions of more than one mole of aluminum halide in ethyl propionate,although remaining liquid and stable over prolonged periods of time,exhibit the disadvantage of a rapid increase in viscosity over a periodof time. For example, at F. (38 C.) the solution doubled in viscosity inless than 2 days. Such viscosity increase makes accurate meteringdifiicult and, more significantly, increases the pumping powerrequirements (decreases pumpabilty) in using the solution. Thesefactors, of course, result in decreased efficiency of a process in whichsuch catalyst solution is used.

It is the discovery of this invention that methyl esters of n-butyric,n-valeric, n-hexanoic, isovaleric, trimethylacetic, 2-methylvaleric,2-ethylbutyric, and 2-ethylhexanoic acids can be used to form aluminumhalide solutions that do not have the aforedescribed viscosity andpumpability disadvantages.

SUMMARY OF THE INVENTION In general, this invention provides a stableliquid aluminum halide catalyst for catalyzing reactions normallycatalyzed by aluminum chloride or aluminum bromide and which has acatalytic activity similar to that of aluminum chloride or bromidealone, that comprises a methyl ester of n-butyric, n-valeric,n-hexanoic, isovaleric, trimethylacetic, Z-methylvaleric,Z-ethylbutyric, or Z-ethylhexanoic acid having dissolved thereinaluminum chloride or aluminum bromide in an amount greater than one moleper mole of said ester.

This invention also provides a method for carrying out a reactioncatalyzed by aluminum chloride or bromide that comprises carrying outsaid reaction in a reaction vessel, under reaction conditions, in thepresence of a catalyst solution comprising aluminum chloride or bromidedissolved in the aforedefined ester in an amount greater than one moleper mole of said ester; separating from the eflluent from said reactionvessel said catalyst solution; and recycling it to the reaction vessel,preferably, with make-up aluminum halide.

BRIEF DESCRIPTION OF THE DRAWING The drawing presents curves on asemi-logarithmic scale showing the relationship between KinematicViscosity at 100 F. and the time in days upon storage of solutions of1.3 moles of AlCl dissolved in ethyl propionate, methyl n-butyrate,methyl n-valerate, and methyl n-hexanoate products.

DESCRIPTION OF SPECIFIC EMBODIMENTS The catalyst of this invention is asolution or complex of an aluminum chloride or bromide in theaforedefined ester. The solution contains more than one mole aluminumchloride or bromide per mole of ester. In general, the amount ofaluminum chloride or bromide dissolved per mole of ester will be betweenabout 1.1 moles and about 1.4 moles. A 1:1 mole solution has little orno catalytic activity. The aluminum chloride or bromide in excess of onemole in the solution appears to be the component that imparts catalyticactivity to the catalyst solution. Thus,

the amount of solution employed to catalyze the reaction will begoverned only by the need to provide sufiicient excess (over one mole)aluminum chloride or bromide to catalyze the desired reaction that isordinarily catalyzed by solid aluminum halide.

The solution of aluminum chloride or bromide in ester is formed readily.A 1:1 mole solution or complex readily forms at room temperature. Thissolution is capable of dissolving additional aluminum chloride orbromide at temperatures of 3050 C. In order to avoid hydrolysis due tomoisture, it is preferred to prepare the catalyst solution in a dryinert atmosphere, such as nitrogen or dry air.

The solvent ester, in accordance with this invention, is the methylester of certain alkanoic acids. The esters are contemplated are methylesters of n-butyric, n-valeric, nhexanoic, isovaleric, trimethylacetic,Z-methylvaleric, 2- ethylbutn'c, and Q-ethylhexanoic acids.

As indicated hereinbefore, the catalyst solution of this invention isutilizable to catalyze any reaction ordinarily catalyzed by solidaluminum chloride or bromide. Such reactions and their operatingconditions are well known in the art. They include alkylation ofaromatic compounds with olefins or aliphatic halides; hydration ofolefins, and isomerization of parafiins.

Of particular interest is the continuous, with catalyst recycle,polymerization of olefins to liquid polymers useful as syntheticlubricants. This invention will be illustrated in connection with thispolymerization. A wide variety of olefins can be polymerized with thestable catalyst solution of this invention. In general, they can containbetween about two and twenty-five carbon atoms per molecule and can bestraight chain or branched chain, with or without aromatic ringsubstituents. Although preferred olefins are the l-olefins, olefinshaving internal double bonds are contemplated. The olefin reactant canbe a single olefin or a mixture of olefins, of which the following arenonlimiting examples: ethylene; butene-l; isobutene; hexene; octene-Z;Z-ethyIheXene-I; decene-Z; decene-l; undecene- 1; dodecene-l;hexadecene-l; octadecene-l; octadecene-9; eicosene; tricosene-l;tetracosene-l; and triacontene-l.

The polymerization is carried out at temperatures of between about 0 C.and about 100 C. for a period of time of about 13 hours. Ordinarily itis carried out at substantially atmospheric pressure, but particularlywith lower olefins, superatmospheric pressures sufficient to maintainliquid phase can be advantageously employed. The amount of catalystemployed will generally be about 1-5 percent, by weight of olefin, basedon excess aluminum chloride. In some operations, in order to renderpolymer products less viscous and more readily handled, a solvent inertto the polymerization can be used. Suitable solvents include keroseneand paraflins, such as heptane, octane, isooctane, decane, etc.

Because the catalyst solution of this invention is a heavy liquid, theeffiuent from the reactor is permitted to stand quiety until the majoramount of the catalyst solution has separated as a lower heavy layer,Alternatively a centrifuge may be used to speed the separation. Thislayer is recycled, with fresh aluminum chloride as needed. Then, theremaining polymer product can be washed free of any residual catalystsolution, dried, and freed of solvent and monomer by distillation.

The following examples demonstrate the preparation of catalyst solutionsof aluminum halide in ethyl propiohate and their use in polymerizingl-olefins. They also show the equivalence of aluminum chloride andaluminum bromide within the contemplation of this invention. Theseexamples appear in copending application Ser. No. 41,709.

EXAMPLE 1 A solution (1) was prepared by dissolving anhydrous aluminumchloride in ethyl propionate at room temperature, in a molar proportion,respectively, of 1.31:1. A week later, a solution (2) was prepared bydissolving 100 g. of decene-l in 50 ml. isooctane and the solutions(1+2) were metered at 0.29 g./min. and 2.49 g./min., respectively over afifty-four minute period, into a flask filled with stirrer, thermometer,and reflux condenser, the mixture in the flask being maintained at50-56" C. After addition of the solutions were complete, the mixture wasmaintained at 5056 C. for an additional hour.

Product work-up was as follows: The reaction mixture was contacted with50 ml. of a 10% aqueous solution of I-ICl and the acid solution wasseparated and removed in a separatory funnel. Then the reaction mixturewas washed (with intermediate phase separation and removal) with 100 ml.water, 125 ml. of 10% aqueous Na CO solution, and then with water untilneutral. The product was dried over Na SO and solvent and monomer wereremoved by distillation. The yield of polymer oil was g. or 90%. It hada K.V. (Kinematic Viscosity) of 29.36 cs. at 210 F. and of 290.9 cs. atF EXAMPLE 2 A large batch of catalyst solution was prepared bydissolving AlCl in ethyl propionate in a molar ratio of 1.31:1,respectively. In order to facilitate solution, the ethyl propionate washeated slightly above room temperature with agitation. This completelyliquid solution was stored in a dry air atmosphere.

EXAMPLE 2A Five days after the large batch solution was prepared, aportion was used to polymerize decene-l using the method ofpolymerization and product workup described in Example 1, at 5056 C.Yield was 90% and the product oil had a K.V. of 33.16 at 210 F. and of347.3 at 100 F.

EXAMPLE 2B Eight days after the large batch solution was prepared, a runwas made at 5153 C. using the proportions of catalyst solution,decene-l, and isooctane as described in Example 1, up to work-up.Instead of washing the reaction mixture, it was placed in a separatoryfunnel, heated to 85 C. and maintained at that temperature whilestanding quietly for about two hours. A used catalyst solution (sludge)separated as a lower layer and 6 decene-l. There was obtained 76.7 g.(76.7%) of a trimer plus oil having the following properties:

K.V. at 210 F., cs. 32.3 K.V. at 100 F., cs. 311.4

was withdrawn. This was stored under dry air and used 5 Viscosity Index153 in subsequent runs. The polymer oil product was washed and i It 90%yield) had a f 3772 at As was indicated hereinbefore, esters other thanethyl 210 F, and of 4102 cs, at 100 propionate were previously foundinefiective to maintain l0 AlCl in solution longer than 24-30 hours.This is demon- EXAMPLE 2C strated in the following example.

Three weeks after the large batch solution was pre EXAMPLE 7 pared, aportion of it (still liquid) was used in a run at 5154 C., using theproportions, procedure, and work- If A $1085 of 0 'f P i y dlssolvlngAlcla up described in Example 1 The Product 90% yield) in variousesters, using slight warming above room temhad a K.V. of 37.72 cs. at210 F. and 410.2 cs. at perature when needed, in a molar proportion of100 F moles AICI per mole ester. Each solution (or mixture) E A 3 wasobserved at room temperature for physical state, i.e., whether liquid(L), solid (S), liquid+solid (L-l-S), On the same days as the run ofExample 2B, a portion immediately after addition of AlCl one hour later,and of the sludge from the run was used in a run to polymtwenty-fourhours later. In the case of the sole effective erize decene-l. It wasfound that the sludge was about a solvent, in the ser es inv g ethylpropionate all 1:1 molar solution of A101 in ethyl propionate.Acobservation was made one month later. Pertinent data cordingly, 0.31mole make-up A1Cl was added per mole are set forth in Table I. ethylpropionate and dissolved. The resultant catalyst solution was used topolymerize decene-l, as described TABLE I in Example 1. The productpolymer 90% yield) had Physical state a K.V. of 47.48 cs. at 210 F. andof 548.0 cs. at 100 F. :53? one 24 one EXAMPLE 5 Ester solvent tion hourhours Month 33253353333: Seventeen and seven tenths grams (0.066 mole)of glg g ggg anhydrous aluminum bromide was dissolved in 5.82 g. 1aietgtm L (0.057 mole) of ethyl propionate (P32657l). A 20.4 Y ace ateg. portion of the above solution and 87 g. (0.62 mole) of 52235 3513233.- l-decene were metered separately and simultaneously S duringseventy-eight minutes into a flask fitted with addiggnzyficletailetltution tubes, stirrer, thermometer, and condenser and main- Y t a e tainedat 30 C. After all components were added, the Ethyl prop 10mm L L L Lmixture was held at 30 C. for one hour. The reaction *Stmng evidence wasi i by pounng onto a mlxture of Ice and hydro- Upon furtherinvestigation, it was found that a class chlonc It was transfeired to asepaiatory funnfil of esters besides ethyl propionate is operative toform Washed W 21.100 Pom9n of Water w 100 solutions, as contemplatedherein, that are liquid for 5% 9 blcarbonate Wm} Water untll neutral anthree days and more. This is illustrated in the following then driedover anhydrous sodium sulfate. The monomer example and dimer wereremoved by distillation at reduced pres- EXAMPI E 8 sure to yield 20.5g. (23.6%) of a trimer plus oil of the followmg Physlcal Propertles: Aseries of solutions was prepared by dissolving o AlCl in various esters,using slight Warming abo ve room temperature where necessary, using amolar ratio of 1.3 I moles AlCl per mole ester. Each solution wasobserved Vlscoslty Index Method 13-2270 initially, at room temperature,for physical appearance. 1267 Those that were liquid were observedperiodically. The EXAMPLE 6 times set forth in Table II reflect thelength of the time period over which each solution was observed and doesThirty-five and four-tenths grams (0.132 mole) of annot indicate thatthe solution became unstable at that hydrous aluminum bromide weredissolved in 11.6 g. time, as the length of the periods of observationvaried.

TABLE II Acid Alcohol Propionate n-Butyrate Valerate n-Hexanoaten-Octanoate n-Nonanoate Methyl.

(0.113 mole) ethyl propionate. A portion of this solution was stored atroom temperature in a dry atmosphere. After five days storage, apolymerization was carried out as described in Example 5, using 23.52 g.of the F stored solution (still liquid) and g. (0.705 mole) of Liquid 2weeks.

VISCOSITY CHANG-E ON STORAGE As has been indicated hereinbefore,aluminum halide solutions in methyl n-butyrate and in methyl n-valerateshow a relatively small change in viscosity upon storage over longperiods of time. On the other hand, solutions in ethyl propionateincrease to a tremendous degree within a rather short period of time.This is demonstrated in the following:

EXAMPLES 9 THROUGH 12 TABLE III Kinematic viscosity at. 100 F.

Eth l Meth l Methyl Meth l propionate n-butyrate n-valerate n-hexanoateTime, days:

Based upon the data in Table III, curves were; plotted showing theviscosity change with time. The drawing presents curves plotted on asemi-logarithmic scale showing the relationship between KinematicViscosity at 100 F. and time in days during storage of a solution of 1.3moles A101 per mole of ethyl propionate (Curve A), of a solution of 1.3moles AlCl per mole of methyl nbutyrate (Curve B), of a solution of 1.3moles AlCl per mole of methyl n-valerate (Curve C), and of a solution of1.3 moles AlCl per mole of methyl n-hexanoate (Curve D). By inspectionof these curves, it will be at once apparent that the solution in ethylpropionate underwent a rapid increase in viscosity, whereas the solutionin methyl esters increased relatively little. For example, in 5 daysethyl propionate solution increased from about 8.5 cs. to about 585 cs.On the other hand, in 5 days, methyl n-butyrate solution increased fromabout cs. to only about 11 cs.

Accordingly, aluminum halide solutions in ethyl propionate can not beused for long without an increase in pumping requirements to move it inrecycle operation, i.e., it becomes less and less pumpable. On the otherhand, solutions in methyl n-butyrate, methyl n-valerate, and methyln-hexanoate remain pumpable. This makes for much more efiicient processoperation.

In previous applications of this series, it has been indicated that theacid portion of the ester solvents must be a normal acid. It isgenerally believed that branchedchain acids are, ineffective, as hasbeen indicated hereinbefore, however, certain branched-chain acid estershave been found to be effective, stable solvents which remainedpumpable. This will be apparent from the following examples:

EXAMPLES 13 THROUGH 17 Five solutions of AlCl each in a differentbranchedchain fatty acid ester, were prepared; each solution containing1.3 moles AlCl per mole of ester. The esters used are indicated in TableIV. 'Each solution was stored at 100 F. over a period of days andperiodically, determinations were made for Kinematic Viscosity at 100 F.(ASTM -D-445). The results of these determinations are set forth inTable IV.

TABLE IV Kinematic viscosity at F., cs.

Methyl Methyl Methyl Methy Tim Methyl trimethyl 2 methyl 2ethyl 2-ethyldays isovalerate acetate valerate butyrate hexanoate From the data inTable IV, it is at once apparent that solutions of aluminum halide inthe esters set forth therein remain stable and pumpable over prolongedperiods. It will also be seen that were the data in Table IV plotted,the curves would be of the same order as curves B, C, and D in thedrawing.

ALKYLATION OF ISOPARAFFINS Another important utilization of the catalystsolutions described herein, is the ethylation, i.e., alkylation ofisobutane. Such ethylation has been found to produce significant amountsof diisopropyl (2,3-dimethylbutane) which has a high blending OctaneNumber. It will be appreci ated that such components having highblending Octane Number without the use of lead, are valuable componentsin lead-free gasolines; and, therefore, contribute to the diminishing ofpollution attributed to leaded gasoline.

Diisopropyl is the kinetc product from acid catalyst ethylation ofisobutane. However, unless reaction conditions are controlled, secondaryreactions present, which result in the formation of C and higherparaffins. Also, cracking with the subsequent addition of ethylene tothe fragments and yield molecules with an odd number of carbon atoms.Such secondary reactions direct from the octane quality of the totaloutput.

The catalysts contemplated for the ethylation process herein describedare solutions of aluminum chloride or aluminum bromide in aconcentration of 1.1 to 1.4 moles aluminum halide per mole of ester. Thecontemplated esters utilizable are those set forth in Tables III and IV.Methyl n-butyrate and methyl n-valerate are preferred.

Although it is not essential, an alkyl halide promoter can be used, suchas ethyl chloride, hydrogen chloride, and t-butyl chloride. The amountof promoter used will be between about 0 and about 0.85 mole promoterper mole of active aluminum halide catalyst. By the term active aluminumhalide reference is made to the amount of the aluminum halide present inthe ester solutions in excess of '1 mole equivalent of ester.

Although the ethylation reaction can be carried out batch-wise, it ismore feasibly and economically carried out in a continuous process. Suchoperation will be utilized in demonstrating the process of thisinvention.

The catalyst concentration will vary between about 1.0 and about 5percent, based upon the isobutane charged. The alkylation temperaturewill be between about 70 F. and about 200 F. The residence time can varywith agitation up to about 60 minutes. The molar ratio of isobutane toethylene will be between about 5 and 10.

The continuous ethylation of isobutane as described in the followingexamples was carried out in a 300 ml. steel autoclave. Moreadvantageously, the reaction can also be practiced in any type reactorwhich will provide intimate mixing such as a thin film reactor. In allruns, the initial ethylene (C pressure and reactor temperature wereestablished. Ethylene flow rate was adjusted to maintain the initialethylene pressure. Then, isobutane and catalyst solution (methyln-butyrate) were metered separately and put simultaneously into thereactor. Residence times were established by pumping rates. The rate ofwithdrawal of efiluent reaction mixture was adjusted to match the rateof addition of fresh isobutane and catalyst. The reaction efiiuent wastransferred to a steel vessel wherein catalyst solution separated bygravity and was withdrawn. Raw alkylate product was permitted to standat room temperature so that almost all unreacted isobutane and ethylenewere removed therefrom, before alkylate analyses were made.

EXAMPLES 17 THROUGH 22 A series of runs were carried out for theethylation of isobutane using the aforedescribed general procedure. Ineach run, conditions were varied within the aforedescribed ranges ofreaction conditions. When a promoter was use, it was ethyl chloride.Pertinent process, conversion, yields and unleaded research OctaneNumber are set forth in Table IV. In Table V the product distribution ofthe alkylate produced in Examples 12 and 13 are set forth.

TABLE IV Example 17 18 19 20 21 22 Temp., F 7 72 200 128 121 120Starting press. (or), p.s.i. 200 so 300 120 150 150 Residence time, min30 30 30 30 30 30 Isobutane/Oz', mol 9. 5 9. 3 9. 7 4. 9 5. G. freeAlCla/lOO g. iC4.- 5.0 2.4 2. 6 5.0 4. 9 Promoter/free A1013, mol 26 .2851 .25 None stirrer, r.p.m 600 600 600 600 1, 000 Ethylene conv., wt.percent. 91. 62.0 61. 9 61.1 78. 5 76. 8 Ca in alkylate, wt. percent 70.0 83.5 78.8 84. 8 76. 9 81. 2 Mini micro RON, clear 99.2 101. 8 99. 5101. 8

* G.C. analysis of washed alkylate.

TABLE V Alkylate composition 8 Example 17 Example 18 1C5 0. 6-0. 6 0.2-0. 2 C 2, gh/iB 60. l 71. 0

a 2.3 l B 7.5 9.4

2-MP 4. 0 0 5. 4 8 2-MP l. 4 2. 0 2,2,3-TMB 0.2 2,3-DMP 0.1 C 2 4-DMP2.0 2.9 0.9 1.4

2-M Hex 0. 4 0.5 3M Hex 0. 2 5-DM Hex 1. 7 1. 3 2,3 fiex-l-2M, 311115}1.3 9 Ca 2,4 ex+2 2 3 2. .7

2,2,4 TM 7. 7 7 3.6 2,3,4 TMP 1. 2 0. 5 2.3 3 TMP 2. 2 1.1 Residue 6.8-6. 8 1. 4-1. 4 Alkylate 99. 2 101.8

RON clear.

8 G.C. analysis of pod bottoms.

Although the present invention has been described with preferredembodiments, it is to be understood that modifications and variationsmay be resorted to, without departing from the spirit and scope of thisinvention, as those skilled in the art will readily understand. Suchvariations and modifications are considered to be within the purview andscope of the appended claims.

What is claimed is:

1. A stable liquid aluminum halide catalyst for catalyzing reactionsnormally catalyzed by aluminum chloride or aluminum bromide and whichhas a catalytic activity similar to that of aluminum chloride or bromidealone, that comprises a methyl ester of n-butyric, nvaleric, n-hexanoic,isovaleric, trimethylacetic, 2-methylvaleric, Z-ethylbutyric or2-ethylhexanoic acid having dissolved therein aluminum chloride oraluminum bromide in an amount greater than one mole per mole of saidester.

2. A liquid catalyst defined in Claim 1, wherein said ester hasdissolved therein between about 1.1 moles and about 1.4 moles aluminumchloride per mole ester.

3. A liquid catalyst defined in Claim 2, wherein said ester is methyln-butyrate.

4. A liquid catalyst defined in Claim 2, ester is methyl nvalerate.

5. A liquid catalyst defined in Claim 2, ester is methyl isovalerate.

6. A liquid catalyst defined in Claim 2, ester is methyltrimethylacetate.

7. A liquid catalyst defined in Claim 2, ester is methyl2-methylvalerate.

8. A method for carrying out a reaction catalyzed by aluminum chlorideor bromide that comprises carrying out said reaction in a reactionvessel, under reaction conditions, in the presence of said catalyst in amethyl ester of n-butyric, n-valeric, n-hexanoic, isovaleric,trimethylacetic, 2 methylvaleric, 2 ethylbutyric, or 2-ethylhexanoicacid in an amount greater than one mole per mole of said ester;separating from the effluent from said reaction vessel said catalystsolution; and recycling it to the reaction vessel with make-up aluminumchloride or bromide.

9. The method defined in Claim 8, wherein said reaction is thepolymerization of olefins.

10. The method defined in Claim 8, wherein said reaction is thealkylation of isobutane with ethylene.

11. A method for polymerizing olefins that comprises contacting, in areaction vessel, said olefins with a catalyst solution of methyln-butyrate having dissolved therein between about 1.1 moles and about1.4 moles aluminum chloride per mole methyl n-butyrate; withdrawing anefiluent stream from said reaction vessel; separating said catalystsolution from said efiluent; and recycling said catalyst solution tosaid reaction vessel with make-up aluminum chloride.

wherein said wherein said wherein said wherein said 12. A method foralkylating isobutane that comprises contacting, in a reaction vessel, amixture of said isobutane and ethylene with a catalyst solution ofmethyl nbutyrate having dissolved therein between about 1.1 moles andabout 1.4 moles aluminum chloride per mole methyl n-butyrate;withdrawing an effluent stream from said reaction vessel; separatingsaid catalyst solution from said effluent; and recycling said catalystsolution to said reaction vessel with make-up aluminum chloride.

References Cited FOREIGN PATENTS 1,433,373 2/1966 France 260683.15

PAUL M. COUGHLAN, Jr., Primary Examiner U.S. Cl. X.R.

' STATES PATENT OFFICE T T CERTIFICATE OF CORRECTION Pltent No.3,833,678 Dated September 3, $97 4 Imremzoflfi JA Q A BRENNAN It iscertified that error appears in the above-identified patent and that aidLetters Patent are hereby corrected as shown below Column t, line 18"quit-1y" should be quiet-1y. w

Column t, line 39 "filled" should be "fitted" Column 8, line 11 "15.5"should be l5. O--.

Column 8, line 37 "lsinetc should be --k;inetic-.

Signed and sealed this 18th day of February 1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officerand Trademarks

